Method of making metal nanostructures using low temperature deposition
A method of forming metal nanostructures is a low temperature closed space vacuum deposition method. The method includes disposing a source material in an enclosed space at low evaporation temperatures to controllably form nanostructures of different dimensionalities on a substrate. The nanostructures have dimensionalities determined by a chosen evaporation temperature. An apparatus is also provided for performing the method.
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The disclosure of the present patent application relates to a method and apparatus useful for making nanostructures, and particularly, to a method and apparatus for making a variety of nanostructures using low temperature closed space vacuum deposition.
2. Description of the Related ArtMetal nanostructures are ubiquitous in basic research and industry. For example, metal nanostructures have been useful in catalysis, sensing, surface-enhanced Raman scattering (SERS), near-infrared photothermal therapy and surface functionalization of various materials.
The properties and function of metal nanostructures are closely correlated with their size, shape, structure and composition. Controlled and consistent synthesis of metal nanostructures for various applications can be energetically and economically costly.
Thus, a method for forming various metal nanostructures using low-temperature vapor deposition and an apparatus for performing said method solving the aforementioned problems are desired.
SUMMARYAn apparatus for making metal nanostructures includes a vacuum chamber and a growth system enclosed within the chamber. The growth system includes a double crucible container and a pair of rods supporting the double crucible container above a bottom surface of the vacuum chamber. The rods can be secured to respective insulators on the chamber floor.
The double crucible container can include an inner crucible, an outer crucible, and a heating element extending between the inner and outer crucibles. Each of the crucibles include a bottom wall, an upright peripheral wall extending from the bottom wall, and an open top end. An upper edge of the inner crucible is bent back, forming a first lip. An upper edge of the outer crucible is also bent back, forming a second lip. A top end of the heating element is also bent and extends beyond the inner and outer crucibles, between the first and second lips. A substrate can be disposed over the open end of the crucibles. A top thermocouple can be disposed over the substrate.
A method for forming nanostructures includes placing an amount of source material in the growth system. The source material can be disposed within a cavity of the inner crucible and the substrate can be disposed over the opening of the inner crucible to form a seal with the lip structure of the inner crucible. A vacuum can be applied towards the growth apparatus within the vacuum chamber and the temperature of the source material can be raised to an evaporation temperature ranging from about 800° C. to about 1350° C. The temperature of the source material can be maintained at the evaporation temperature for a period of time. The source material can be allowed to cool to room temperature and the vacuum can be released. The nanostructures can be deposited on the substrate and take a form depending on the evaporation temperature chosen, e.g., the substrate temperature relative to the melting temperature of the source material chosen.
These and other features of the present subject matter will become readily apparent upon further review of the following specification.
Similar reference characters denote corresponding features consistently throughout the attached drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTSThe double crucible container 20 can include an inner crucible 22, an outer crucible 24, and a heating element 23 extending between the inner and outer crucibles 22, 24. Each of the crucibles 22, 24 include a bottom wall 31, an upright peripheral wall 29 extending from the bottom wall 31, and an open top end. An upper edge of the inner crucible 22 is bent back, forming a first lip 35. An upper edge of the outer crucible is also bent back, forming a second lip 37. A top end of the heating element 23 extends beyond the inner and outer crucibles 22, 24, between the first and second lips, 35, 37. A substrate 40 can be placed over the open end of the inner crucible 22 and a top thermocouple 25 can be placed over the substrate 40. A source material 45 can be disposed within a cavity of the inner crucible, as illustrated in
The inner crucible and outer crucible can be made from materials having high thermal conductivity, compressive strength, thermal shock resistance; and low thermal expansion and reactivity. Suitable materials may include, for example, ceramics and alumina. In a particular embodiment, the inner crucible and outer crucible each include alumina. The inner crucible can be smooth. The heating element can be in direct contact with the outer surface of the inner crucible and an inner surface of the outer crucible. In an embodiment, the rods are stainless steel rods.
The inner crucible and outer crucible can have any suitable shape, such as barrel-shaped, conical-shaped, and cylindrical-shaped. Barrel-shaped crucibles can have an open end with a top diameter that is essentially the same as or only slightly smaller than the diameter of the bottom wall. The peripheral walls can bulge out, producing a barrel shaped crucible. Conical or tapered crucibles can have an opening with a diameter that is larger than a diameter of the bottom wall and a cone-shaped peripheral wall (as illustrated in
The substrate may be chosen according to the ultimate application for which the metal nanostructures are being made. For example, the substrate may be silicon, glass or quartz. In an embodiment, the substrate is a silicon substrate, such as a silicon wafer. The substrate can be of a shape and size capable of completely covering the opening of the inner crucible forming a seal with the lip of the inner crucible. The substrate may comprise a semiconducting material, in an embodiment.
The heating element can be a resistive wire or similar element. The heating element may be disposed around an outer surface of the inner crucible. In a particular embodiment, the heating element is a tungsten wire. The heating element can be connected to a power source for applying a voltage across the heating element.
The top thermocouple can be attached to the outer surface of the substrate and a bottom thermocouple can be attached to a bottom of the outer crucible. The top thermocouple can determine a temperature of the substrate and the bottom thermocouple can determine a temperature of the source material.
The vacuum chamber can be connected to a high-vacuum system capable of achieving a vacuum pressure of 10−4-10−6 mbar, e.g., 10−5 mbar. The vacuum chamber may be approximately an order of magnitude larger than the double crucible container in linear scale. For example, a height (y) of the vacuum chamber can be about 25 cm and a width (x) of the vacuum chamber can be about 20 cm. The power source may be external to and electrically isolated from the vacuum chamber.
A method for forming nanostructures can include low temperature closed space vacuum vapor deposition (LT-CSVVD). The method can include placing an amount of source material in the cavity of the inner crucible. The source material can be in solid form, for example, in the form of a powder or grain. The source material may have an average size that is less than about 2.0 mm, for example, an average size ranging from about 0.5 mm to about 1.0 mm. The amount of source material may vary, ranging from about 3 mg to about 15 mg. About 3 mg to about 5 mg of the source material can be disposed in the cavity to form a nanostructure film. About 10 mg to about 15 mg of the source material can be disposed in the cavity to form nanostructures in thick film or powder form. The growth apparatus can be closed by placing the substrate on the lip of the inner crucible.
The substrate can be rinsed and dried before covering the container. For example, the substrate can be rinsed with the following solvents in order: distilled water, ethanol, distilled water, ethanol, semiconductor detergent, and ethanol. The substrate may be dried by any known means, such as by air evaporation.
Once the growth system is disposed in the high vacuum chamber, the heating element can be connected with the power source and a high vacuum can be applied. The high vacuum can range from about 10−4 mbar to about 10−6 mbar, e.g., 10−5 mbar. A temperature of the source material can be raised to an evaporation temperature of 850° C.-1350° C., depending on the desired nanostructure to be grown (
The term nanostructures, as used herein, refers to materials having a dimension of a nanoscale range, which may be from 1 to 999 nm. e.g., 1.100 nm. Nanostructures include, for example, zero dimensional (0D) nanostructures, i.e., nanoparticles; one dimensional (1D) nanostructures, i.e., nanowires or nanotubes; and two dimensional (2D) nanostructures, i.e., nanosheets or nanoflakes For example, a nanosheet is a nanostructure with at least one nanoscale dimension (thickness). A nanoparticle is a nanostructure with all three dimensions being nanoscale.
The amounts of materials for the methods described herein are exemplary, and appropriate scaling of the amounts are encompassed by the present subject matter, as long as the relative ratios of materials are maintained. As used herein, the term “about,” when used to modify a numerical value, means within ten percent of that numerical value. The following examples illustrate the present teachings.
EXAMPLES Example 1 Exemplary Apparatus for Present Method3 mg-15 mg of the source material (in the form of grain or powder, 0.5 mm-1.0 mm in diameter) was placed in the bottom of the growth apparatus of Example 1, as shown in
The surface morphology of the nanostructures prepared according to the present method was observed with a field emission scanning electron microscope (FE-SEM) (JEOL JSM-6700F). Samples for FESEM analysis were prepared over an area of 3×3 mm2. X-ray diffraction (XRD) data were collected using an x-ray diffractometer (Shimadzu XRD-6100) with Cu-Kα radiation. The measurements ranged from 2θ=10° to 2θ=65° with a scanning speed of 0.02°/sec at 40 kV and 30 mA. The incident wavelength was 1.54060 Å, and I/Io was 0.5. Crystallographic structure analysis of nanomaterials was investigated by a crystallographic Rietveld program.
The evaporation temperature of the source materials (Tso) and the temperature of the substrate (Ts) were critical for the growth of the nanostructures. The evaporation temperature was changed from 850° C. up to 1350° C., which alone caused a change in the obtained nanostructure dimensions. At low temperature, zero-dimensional nanostructure, such as nanoparticles, were grown. At higher temperature, one-dimensional nanostructures, such as nanowires, were grown.
As an initial example, Ge nanostructures were prepared according to the conditions of Table 1, resulting in the structures shown in
Considering the Ge and Al nanostructures and data of Tables 1 and 5, growth of different nanostructures may depend on the substrate temperature, Ts, relative to the melting temperature of the source material, Tm. In the exemplary implementations discussed above, Tm is 1064.18° C., 938.25° C. and 660.32° C. for Au, Ge and Al, respectively. The substrate temperature should range between Tm/2 and Tm/4, in an embodiment, to produce a resulting nanostructure growth. The substrate temperatures tested were 280° C., 330° C., 380° C. and 420° C. for the Au nanostructures formed (where Tm/4=266.05° C. and Tm/2=532.09° C.); 240° C., 270° C. and 380° C. for the Ge nanostructures formed (where Tm/4=234.56° C. and Tm/2=469.13° C.); and 210° C. for the Al nanostructures formed (where Tm/4=125.08° C. and Tm/2=330.16° C.). For example, when Ts/Tm=0.28>0.25, the energy for growing the 1D is not sufficient, and small nanoparticles are grown from limited neighbor nucleant sites. Increasing the substrate temperature may slightly increase the mobility of nuclei, which combine to become larger nanoparticles. Since 0.25<Ts/Tm=0.34 or 0.39<0.5 at the temperatures tested, some particles condense for a short time to form droplets on the substrate and become nuclei for 1D growth. The present methods and apparatus would be expected to work for materials other than the presently tested Au, Ge and Al. In particular, other metals including, e.g., Cr, Fe, Co. Ni, Cu, Zn, Cd, Sn, Ti, should be potentially usable in the present method.
It is to be understood that the present method and apparatus are not limited to the specific embodiments described above, but encompasses any and all embodiments within the scope of the generic language of the following claims enabled by the embodiments described herein, or otherwise shown in the drawings or described above in terms sufficient to enable one of ordinary skill in the art to make and use the claimed subject matter.
Claims
1. A method for forming nanostructures comprising the steps of:
- providing an apparatus for forming nanostructures from a source material, the apparatus comprising: a) a vacuum chamber; b) a double crucible container within the vacuum chamber, the double crucible container including: i) an outer crucible having a bottom wall, an upright peripheral wall extending from the bottom wall and forming a lip at an upper end thereof, an open top end opposite the bottom wall, and an inner cavity, ii) an inner crucible disposed within the inner cavity of the outer crucible, the inner crucible including a bottom wall, an upright peripheral wall extending from the bottom wall and forming a lip at an upper end thereof, an open top end opposite the bottom wall, and an inner cavity for receiving a source material, the lip of the inner crucible being configured to support a substrate over the open top end of the inner crucible, and iii) a resistive heating element extending between the outer crucible and the inner crucible, the heating element configured to surround an outer surface of the peripheral wall of the inner crucible
- placing an amount of source material in the cavity of the inner crucible of the apparatus, the source material having a melting temperature, wherein the source material is selected from the group consisting of Au, Ge, Al Cr, Fe, Co, Ni, Cu, Zn, Cd, Sn, and Ti;
- placing the substrate over the open end of the inner crucible to form a seal with the lip structure of the inner crucible;
- applying a vacuum to the vacuum chamber;
- raising a temperature of the source material to an evaporation temperature and a temperature of the substrate to a substrate temperature over a first period of time;
- maintaining the source material at the evaporation temperature and the substrate at a substrate temperature for a second period of time;
- forming nanostructures on the substrate; and
- allowing the source material to cool to room temperature.
2. The method of claim 1, wherein a vacuum pressure of the vacuum ranges from about 10-4 mbar to about 10-6 mbar.
3. The method of claim 1, wherein the evaporation temperature ranges from about 850° C. to about 1350° C.
4. The method of claim 1, wherein the source material is Au.
5. The method of claim 4, wherein the evaporation temperature ranges from about 1100° C. to about 1300° C. and the nanostructures comprise nanoparticles having a diameter ranging from about 50 nm to about 100 nm.
6. The method of claim 4, wherein the evaporation temperature is about 1350° C. and the nanostructures comprise nanoparticles having a diameter ranging from about 100 nm to about 200 nm and nanowires having a diameter that is less than about 100 nm.
7. The method of claim 1, wherein the source material is Ge.
8. The method of claim 7, wherein the evaporation temperature ranges from about 900° C. to about 1150° C. and the nanostructures comprise nanowires having a diameter ranging from about 500 nm to about 1000 nm.
9. The method of claim 7, wherein the evaporation temperature ranges from about 1200° C. to about 1300° C. and the nanostructures comprise nanowires having a diameter less than about 200 nm.
10. The method of claim 1, wherein the source material is Al.
11. The method of claim 10, wherein the evaporation temperature ranges from about 800° C. to about 900° C. and the nanostructures comprise nanowires having a diameter ranging from about 50 nm to about 150 nm.
12. The method of claim 1, wherein the source material is a powder or grain having a diameter less than 2 mm on average.
13. The method of claim 1, wherein the amount of source material ranges from about 3 mg to about 15 mg.
14. The method of claim 1, wherein the substrate comprises silicon.
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Type: Grant
Filed: Apr 3, 2021
Date of Patent: Feb 8, 2022
Assignee: KING FAISAL UNIVERSITY (Al-Ahsa)
Inventors: Nagih Mohammed Shaalan (Al-Ahsa), Faheem Ahmed (Al-Ahsa), Osama Sabera (Al-Ahsa), Dalia Hamad (Al-Ahsa), Abdullah Aljaafari (Al-Ahsa), Adil Alshoaibi (Al-Ahsa)
Primary Examiner: Kelly M Gambetta
Application Number: 17/221,786
International Classification: C23C 14/24 (20060101); C23C 14/16 (20060101); C23C 14/26 (20060101); C23C 14/54 (20060101); B82Y 30/00 (20110101); B82Y 40/00 (20110101);